Unit:
Κατεύθυνση Οργανική Σύνθεση και Εφαρμογές της στη Χημική ΒιομηχανίαLibrary of the School of Science
Author:
Doukas Konstantinos
Supervisors info:
Αθανάσιος Γκιμήσης Αναπληρωτής Καθηγητής
Θωμάς Μαυρομούστακος Καθηγητής
Alessandro Venturini Senior Researcher
Original Title:
Theoretical investigation of the mechanism involved in the reaction of N-hydroxy-urea and amide derivatives with phosgene in pyridine.
Translated title:
Theoretical investigation of the mechanism involved in the reaction of N-hydroxy-urea and amide derivatives with phosgene in pyridine.
Summary:
The objective of this thesis was theoretical study of a reaction that has been developed in the supervisor's laboratory during a doctoral thesis. The reaction of a series of N-hydroxyurea derivatives of amino acids in the presence of trisphosgene, in pyridine, led to the formation of 2-aminoxy[1,2-a][1,3,5]-triazine-2,4-diones. This unprecedented products arise from the addition of the N-hydroxyurea nitrogen to the 2 position of pyridine, followed of preceded by a trisphosgene carbonyl mediated bridge formation between the pyrisine and amino acid nitrogens.
The purpose of this study was to investigate theoretically the possible mechanistic pathways of the above reaction, in order to determine the potential energy map of the reaction as well as of possible extentions of the methodology. This investigation consists of a thorough examination of all possible intermediates and transition states. that take part in the proposed mechanism. More specifically the intermediates were optimized to their lowest energy conformation. For the transition states (TSs) an initial hypothetical structure was drawn, and after optimization and frequencies calculation the ideal TSs were produced.
As for the results of all thsese studies a series of optimized intermediates were determined which lead to the final observred product through a minimal energy pathway. At the same time the building blocks of a general system that leads through a novel reaction scheme to 2-substituted pyridines was determined. All experiments were performed at various levels of the Density Functional Theory method with the use of Gaussian-09w package.
Main subject category:
Science
Keywords:
2-aminoxy[1,2-a][1,3,5]triazine-2,4-diones, mechanism of formation, intermediate energy optimization, transition state energy, DFT
File:
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Thesis - Αντιγραφή - Αντιγραφή - Αντιγραφή-converted.pdf
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